JP3530530B2 - Fuel additive composition containing poly (oxyalkylene) amine and polyalkylhydroxyaromatic - Google Patents

Abstract

There is disclosed a process for the preparation of a polyisobutyl hydroxyaromatic compound wherein the polyisobutyl substituent has an average molecular weight in the range of 400 to 5000, which comprises alkylating a hydroxyaromatic compound in the presence of an alkylation catalyst with a suitable polyisobutene containing at least 70% of a methyvinylidene isomer.

Description

TECHNICAL FIELD The present invention relates to a fuel additive composition. Specifically, the present invention relates to fuel additive compositions containing poly (oxyalkylene) amines and polyalkyl hydroxyaromatic compounds.

[Background technology]

It is well known in the art that liquid hydrocarbon fuels such as fuel oils and gasoline tend to exhibit certain deleterious properties after long term storage or under actual operating conditions. For example, gasoline during operational use tends to deposit sludge and varnish at various points on power plants, including carburetors or fuel injectors and suction valves. Therefore, it is desirable to find a way to improve liquid hydrocarbon fuels by reducing the tendency to leave such deposits.

U.S. Pat.No. 3,849,085 discloses a gasoline boiling range hydrocarbon in which the aliphatic hydrocarbon radical contains about 0.01 to 0.25 vol% high molecular weight aliphatic hydrocarbon-substituted phenol having an average molecular weight in the range of about 500 to 3,500. A motor fuel composition comprising a mixture is disclosed. This patent
An engine designed such that a gasoline composition containing a small amount of an aliphatic hydrocarbon-substituted phenol not only prevents or prevents deposit formation at the intake valve and inlet of a gasoline engine, but also operates at higher operating temperatures. To improve the performance of the fuel composition therein and to minimize cracking and deposit formation in the engine manifold.

U.S. Pat. No. 4,134,846 discloses (1) a reaction product of an aliphatic hydrocarbon substituted phenol, epichlorohydrin, and a primary or secondary mono- or poly-amine,
(2) A fuel additive composition comprising a mixture with polyalkylenephenol is disclosed. This patent teaches that such compositions exhibit excellent cleanability for carburetors, suction devices and combustion chambers, yet provide effective rust protection when used in hydrocarbon fuels at low concentrations. .

[Disclosure of Invention]

The present invention comprises (a) a poly (oxyalkylene) amine having at least one basic nitrogen atom, a sufficient number to render the poly (oxyalkylene) amine soluble in hydrocarbons boiling in the gasoline or diesel range. A poly (oxyalkylene) amine having an oxyalkylene unit, and (b) a polyalkylhydroxyaromatic compound or a salt thereof, wherein the polyalkyl group is a hydrocarbon boiling in the gasoline or diesel range. There is provided a novel fuel additive composition comprising a polyalkylhydroxy aromatic compound or a salt thereof having a molecular weight and a carbon chain length sufficient to make benzene soluble.

The present invention further provides a fuel composition comprising a large amount of hydrocarbons boiling in the gasoline or diesel range and a detergent effective amount of the novel fuel additive composition described above.

The present invention is directed to a fuel concentra consisting of an inert stable lipophilic organic solvent boiling in the range of about 150 ° F to 400 ° F and about 10-70% by weight of the fuel additive composition of the present invention.
te).

Among the various factors, the present invention provides that the unique combination of poly (oxyalkylene) amine and polyalkyl hydroxyaromatic compound provides unexpectedly superior deposit control performance when compared to each component individually. Is based on the amazing finding that says to give.

[Detailed Description of the Invention]

Poly (oxyalkylene) amine As mentioned above, the poly (oxyalkylene) amine of the fuel additive composition of the present invention comprises at least one basic nitrogen atom and a poly (oxyalkylene) amine that boils in the gasoline or diesel range. It is a poly (oxyalkylene) amine having a sufficient number of oxyalkylene units to make it soluble in hydrocarbons. Such poly (oxyalkylene) amines preferably have sufficient molecular weight to be non-volatile at normal engine intake valve operating temperatures, which are generally in the range of about 175 ° C to 300 ° C.

In general, suitable poly (oxyalkylene) amines for use in the present invention are at least about 5 units of oxyalkylene units, preferably about 5-100 units, more preferably about 8-100 units, even more preferably about 10 units. Contains ~ 100 units. A particularly preferred poly (oxyalkylene) amine contains about 10 to 25 oxyalkylene units.

The molecular weight of the poly (oxyalkylene) amines currently used is generally about 500 to about 10,000, preferably about 500.
~ In the range of about 5,000.

Suitable poly (oxyalkylene) amine compounds are, for example, hydrocarbyl poly (oxyalkylenes) such as those described in US Pat. No. 4,247,301 to Honnen, which is incorporated herein by reference. ) Polyamines are included. These compounds have at least one hydrocarbyl terminated poly (oxyalkylene) chain of oxyalkylene units in which the poly (oxyalkylene) moiety has 2 to 5 carbon atoms, and the poly (oxyalkylene) chain has a terminal carbon atom. 2 through the atom
A hydrocarbyl poly (oxyalkylene) polyamine attached to a nitrogen atom of a polyamine having about 12 amine nitrogen atoms and 2 to about 40 carbon atoms and a carbon to nitrogen ratio of about 1: 1 to 10: 1. is there. The hydrocarbyl group of these hydrocarbyl poly (oxyalkylene) polyamines has about 1 to 30 carbon atoms. These compounds generally have a molecular weight in the range of about 500 to 10,000, preferably about 500 to 5,000, more preferably about 800 to 5,000.

The hydrocarbyl poly (oxyalkylene) polyamines described above are prepared by conventional methods known in the art, eg, as taught in US Pat. No. 4,247,301.

Other poly (oxyalkylene) amines suitable for use in the present invention are those in which the poly (oxyalkylene) moiety is attached to the polyamine moiety through an oxyalkylene hydroxy-type bond derived from an epihalohydrin such as epichlorohydrin or epibromohydrin. Is a poly (oxyalkylene) polyamine. Such poly (oxyalkylene) amines having epihalohydrin-derived linkages are described, for example, in US Pat. No. 4,261,704, which description is incorporated herein by reference.

Polyamines useful for making epihalohydrin-derived poly (oxyalkylene) polyamines include, for example, alkylene polyamines, polyalkylene polyamines, cyclic amines such as piperazine, and amino-substituted amines. Poly (oxyalkylene) polyamines having an epihalohydrin-derived bond between the poly (oxyalkylene) and polyamine moieties are described, for example, in US Pat.
Manufactured using known methods as taught in 1,704.

Another class of poly (oxyalkylene) s useful in the present invention
Amine is a highly branched alkyl poly (oxy), as described, for example, in European Patent Application No. 0,448,365 A1 published September 25, 1991, the description of which is hereby incorporated by reference. Alkylene) monoamine. These highly branched alkyl poly (oxyalkylene) monoamines have the general _{formula: RO [C 4 H 8 O} ] xCH 2 CH 2 CH 2 NH 2 ( wherein, R, 12 to 40 amino A highly branched alkyl group having carbon atoms, preferably an alkyl group having 20 carbon atoms derived from a Guerbet condensation reaction,
x is a number up to 30, preferably 4-8).

Preferred alkyl groups are derived from Guerbet alcohols having 20 carbon atoms having the formula: Where R ″ is a hydrocarbyl chain.

The above highly branched alkyl poly (oxyalkylene) monoamines are described, for example, in European Patent Application No. 0,448,365.
Manufactured using known methods, as described in A1.

Preferred classes of poly (oxyalkylene) amines suitable for use in the compositions of the present invention include, for example, U.S. Patent Nos. 4,288,612, 4,236,020, 4,160,648,
No. 4,191,537, No. 4,270,930, No. 4,233,168, No. 4,1
The hydrocarbyl-substituted poly (oxyalkylene) amino carbamates described in 97,409, 4,243,798, and 4,881,945, the descriptions of which are hereby incorporated by reference. These hydrocarbyl poly (oxyalkylene) aminocarbamates have at least one basic nitrogen atom and have an average molecular weight of about 500 to 10,000, preferably about 500 to 5,000, more preferably about 1,000 to 3,000. As described in more detail below, these hydrocarbyl poly (oxyalkylene) aminocarbamates can be said to include a poly (oxyalkylene) component, an amine component, and a carbamate linking group.

A. Poly (oxyalkylene) Component The hydrocarbyl-terminated poly (oxyalkylene) polymer used to make the aminocarbamate used in the present invention is a monohydroxy compound, such as an alcohol often referred to as a monohydroxy polyether. ,
Or polyalkylene glycol monocarbyl ether,
Or "end-capped" poly (oxyalkylene) glycols, which should be distinguished from non-hydrocarbyl terminated, i.e. non-endcapped poly (oxyalkylene) glycols (diols) or polyols. Hydrocarbyl terminated poly (oxyalkylene) alcohols are prepared by the addition of lower alkylene oxides such as oxirane, ethylene oxide, propylene oxide, butylene oxide, etc., to hydroxy compounds, ROH, under polymerization conditions, where R is a poly It is a hydrocarbyl group for end-capping a (oxyalkylene) chain. The radical R of the poly (oxyalkylene) component used in the present invention is generally from 1 to
It has about 30 carbon atoms, preferably 2 to about 20 carbon atoms, preferably aliphatic or aromatic, i.e. alkyl or alkylphenyl, where alkyl has 1 to about 24 carbon atoms. It is a chain or a branched chain. More preferably R is a branched chain in which the alkyl group has 12 carbon atoms derived from propylene tetramer and is commonly referred to as tetrapropenyl. The oxyalkylene units of the poly (oxyalkylene) component preferably have from 2 to about 5 carbon atoms, although one or more units having a higher carbon number may be present. Generally, each poly (oxyalkylene) polymer comprises about 5 units of oxyalkylene units, preferably about 5 to about 100 units of oxyalkylene units, more preferably about 8 to about 100 units, even more preferably about 10 to 100 units. Units, most preferably 10 to
It has about 25 units of oxyalkylene units. The poly (oxyalkylene) component used in the present invention is described in US Pat.
4,191,537, the description of which is hereby incorporated by reference, is more fully described and exemplified.

The hydrocarbyl groups of the hydrocarbyl poly (oxyalkylene) component preferably have from 1 to about 30 carbon atoms, although longer hydrocarbyl groups, especially longer chain alkylphenyl groups, can also be used.

For example, US Pat. No. 4,8 by Buckley.
It is also contemplated to use in the present invention an alkylphenyl poly (oxyalkylene) aminocarbamate where the alkyl group has at least 40 carbon atoms, as described in 81,945. U.S. Pat.No. 4,881,945
The alkyl phenyl group of the aminocarbamate of the specification comprises an alkyl group preferably having 50 to 200 carbon atoms, more preferably an alkyl group having 60 to 100 carbon atoms. The description of U.S. Pat. No. 4,881,945 is hereby incorporated by reference.

The alkyl group is C ₈ -C ₂₀ as described in PCT International Patent Application Publication No. WO 90/07564 published July 12, 1990, the description of which is hereby incorporated by reference. α
About derived from α-olefin oligomers of olefins
Alkylphenyl poly (oxypropylene) aminocarbamates, which are substantially linear alkyl groups having 25 to 50 carbon atoms, are also contemplated for use in the present invention.

B. Amine Component The amine portion of the hydrocarbyl terminated poly (oxyalkylene) aminocarbamate is preferably derived from a polyamine having 2 to about 12 amine nitrogen atoms and 2 to about 40 carbon atoms. The polyamine preferably reacts with a hydrocarbyl poly (oxyalkylene) chloroformate to produce a hydrocarbyl poly (oxyalkylene) aminocarbamate fuel additive that can be used within the scope of the present invention. The chloroformate itself is derived from a hydrocarbyl poly (oxyalkylene) alcohol by reaction with phosgene. Polyamines, including diamines, have, on average, at least about 1 basic nitrogen atom per carbamate molecule,
That is, it provides a poly (oxyalkylene) aminocarbamate product having a nitrogen atom that can be titrated with a strong acid. The polyamine preferably has a carbon to nitrogen ratio of about 1: 1 to about 10: 1. Polyamines include hydrogen, hydrocarbyl groups having 1 to about 10 carbon atoms, acyl groups having 2 to about 10 carbon atoms, and monoketones, monohydroxy, of hydrocarbyl groups having 1 to 10 carbon atoms,
It may be substituted with a substituent selected from mononitro, monocyano, alkyl, and alkoxy derivatives. At least one of the basic nitrogen atoms of the polyamine is preferably a primary or secondary amino nitrogen. The polyamine component used in the present invention is more fully described and exemplified in US Pat. No. 4,191,537.

Hydrocarbyl used in the present invention to describe poly (oxyalkylene) and amine components, hydrocarbyl refers to organic radicals consisting of carbon and hydrogen, which are aliphatic, cycloaliphatic, aromatic or combinations thereof. , For example, aralkyl. Preferably, the hydrocarbyl groups are relatively aliphatic unsaturated, ie free of ethylenic and acetylenic, especially acetylenic unsaturation. More preferred polyamines that can be used within the scope of the present invention are alkylenediamines and substituted polyamines, such as polyalkylenepolyamines, including alkyl and hydroxyalkyl substituted polyalkylenepolyamines. Preferably the alkylene group has 2 to 6 carbon atoms and there are preferably 2 to 3 carbon atoms between the nitrogen atoms. Examples of such polyamines include ethylenecyamine, diethylenetriamine, triethylenetetramine, di (trimethylene) triamine, dipropylenetriamine, tetraethylenepentamine and the like. Of the polyalkylene polyamines, polyethylene polyamines and polypropylene polyamines having 2 to 12 amine nitrogen atoms and 2 to 24 carbon atoms are particularly preferred, especially lower polyalkylene polyamines such as ethylenediamine, diethylenetriamine, propylenediamine, diamine. Most preferred is propylene triamine and the like.

C. Aminocarbamate The poly (oxyalkylene) aminocarbamate fuel additive used in the composition of the present invention comprises a carbamate bond between an amine component and a poly (oxyalkylene) component, ie, [Wherein, oxygen can be regarded as the terminal hydroxyl oxygen of the poly (oxyalkylene) alcohol component, and the carbonyl group -C (O)-is preferably provided by a coupling agent, for example, phosgene] It is obtained by binding to. In a preferred method of preparation, hydrocarbyl poly (oxyalkylene) alcohol is reacted with phosgene to form a chloroformate, which chloroformate is reacted with a polyamine. The carbamate bond is formed when the poly (oxyalkylene) chain is attached to the nitrogen of the polyamine by the oxycarbonyl group of the chloroformate. Since the polyamine may have more than one nitrogen atom capable of reacting with the chloroformate, the aminocarbamate is defined as at least one hydrocarbyl poly (oxyalkylene group attached to the nitrogen atom of the polyamine by a hydrocarbyl group. ) Although containing a polymer, the carbonate may contain 1-2 or more such chains. The hydrocarbyl poly (oxyalkylene) aminocarbamate product preferably contains, on average, about 1 poly (oxyalkylene) chain per molecule (ie, is a monocarbamate), although the reaction pathway is It will be appreciated that the polyamines having reactive nitrogen atoms may result in a mixture having an appropriate amount of di or higher poly (oxyalkylene) chain substituents.
A particularly preferred aminocarbamate is an alkylphenyl poly (oxybutylene) aminocarbamate where the amine moiety is derived from ethylenediamine or diethylenetriamine. Synthetic methods, preparation methods, and other properties of the aminocarbamates used in the present invention that avoid higher degrees of substitution are more fully described and exemplified in US Pat. No. 4,191,537.

Polyalkylhydroxyaromatic compound As mentioned above, the polyalkylhydroxyaromatic component of the fuel additive composition of the present invention is a polyalkylhydroxyaromatic compound or salt thereof, in which case the polyalkyl group is It has a molecular weight and carbon chain length sufficient to render the polyalkyl hydroxyaromatic compound soluble in hydrocarbons boiling in the gasoline or diesel range. Similar to the poly (oxyalkylene) amine component of the present invention, the polyalkyl hydroxyaromatic compound generally has a temperature of about 175 ° C.
It is preferably of sufficient molecular weight to be non-volatile at normal engine inlet valve operating temperatures in the range of ~ 300 ° C.

Generally, the polyalkyl substituent of the polyalkyl hydroxyaromatic compound is about 400 to 5,000, preferably about 400 to
It has an average molecular weight in the range of 3,000, more preferably about 600-2,000.

The polyalkyl-substituted hydroxyaromatic compounds that can be used in the present invention are derived from hydroxyaromatic hydrocarbons. Such hydroxyaromatic compounds include 1
Included are mononuclear monohydroxy and polyhydroxy aromatic hydrocarbons having -4, preferably 1-3 hydroxy groups. Suitable hydroxy aromatic compounds include phenol, catechol, resorcinol, hydroquinone, pyrogallol and the like. The preferred hydroxyaromatic compound is phenol.

Suitable polyalkyl hydroxyaromatic compounds and methods for their preparation are described, for example, in U.S. Patent No. 3,849,085,
4,231,759 and 4,238,628 (their descriptions are included here for reference).

The polyalkyl substituents of the polyalkylhydroxyaromatic compounds used in the present invention are generally derived from polyolefins that are polymers or copolymers of monoolefins, especially 1-mono-olefins such as ethylene, propylene, butylene. can do. The mono-olefin used preferably has 2 to about 24 carbon atoms, more preferably about 3 to 12 carbon atoms. More preferred mono-olefins include propylene, butylene,
In particular isobutylene, 1-octene and 1-decene are included. Polyolefins made from such mono-olefins include polypropylene, polybutene, especially polyisobutene, and poly alpha olefins formed from 1-octene and 1-decene.

The preferred polyisobutenes used to make the currently used polyalkylhydroxyaromatic compounds contain at least about 20%, preferably at least 50%, more preferably at least 70% of the more reactive methylvinylidene isomer. It is polyisobutene. Suitable polyisobutenes include those made with a BF ₃ catalyst. Methylvinylidene isomer is a large percentage of the total composition
A method of making such polyisobutenes, which occupy the following categories, is described in US Pat. Nos. 4,152,499 and 4,605,808.

An example of a suitable polyisobutene having a high alkylvinylidene content is British Petroleum (Br
Ultravis 30, available from Itish Petroleum, including polyisobutene having a molecular weight of about 1300 and a methylvinylidene content of about 74%.

Numerous methods are known for making the polyalkylhydroxyaromatic compounds used in the present invention, any of which are suitable for making the polyalkylhydroxyaromatic component of the fuel additive composition of the present invention. it is conceivable that. One such method is U.S. Pat. No. 3,849,085.
Aluminum chloride, as described in
A method of reacting an olefin polymer with phenol in the presence of a sulfuric acid catalyst is included. Similarly, U.S. Pat.
No. 759 discloses that polyalkyl hydroxyaromatic compounds can be obtained by alkylation of phenols with polypropylene, polybutylene, and other polyalkylene compounds in the presence of alkylation catalysts such as boron trifluoride. Has been done.

One preferred method of making polyalkyl hydroxyaromatic compounds is disclosed in US Pat. No. 4,238,628. This patent teaches a method of making undegraded alkylated phenols by alkylating a complex of boron trifluoride and phenol with a higher olefin polymer having propylene or terminal ethylene units at about 0 ° C to 60 ° C. Where the molar ratio of complex to olefin polymer is about 1: 1 to 3: 1. Preferred olefin polymers include polybutenes having terminal ethylene units.

Preferred polyalkyl hydroxyaromatic compounds that can be used in the fuel additive composition of the present invention include polypropylene phenol, polyisobutylene phenol,
And polyalphaphenols, especially polyalkylphenols derived from 1-decene oligomers.

Polyalkylphenols in which the polyalkyl group is derived from poly-alpha-olefins such as 1-octene and 1-decene oligomers are disclosed in PCT published July 12, 1990.
International Patent Application Publication No. WO 90/07564 (the description of which is included here for reference). This publication
Such polyalkylphenols can be prepared by reacting a suitable polyalphaolefin with phenol in the presence of an alkylation catalyst either neat or in an inert solvent at atmospheric pressure at a temperature of about 60 ° C to 200 ° C. I am teaching. A preferred alkylation catalyst for this reaction is Amberlyst 15 available from Rohm and Haas Company, Philadelphia, PA.
A sulfonic acid catalyst such as (registered trademark).

Salts of polyalkylhydroxyaromatic components such as alkali metal, alkaline earth metal, ammonium, substituted ammonium and sulfonium salts are also contemplated for use in the fuel additive composition of the present invention. Preferred salts are alkali metal salts of polyalkyl hydroxyaromatic compounds, especially sodium and potassium salts, and substituted ammonium salts.

Fuel Compositions The fuel additive compositions of the present invention are generally used in hydrocarbon distillate fuels boiling in the gasoline or diesel range. The appropriate concentration of this additive composition required to achieve the desired cleanability and dispersibility will depend on the type of fuel used, other detergents, dispersants, and the presence of other additives. To do. However, in general, to achieve the best results, 150-7500 ppm by weight of base fuel, preferably 300-2500 ppm of additive composition of the present invention is required.

With respect to the individual components, fuel compositions containing the additive composition of the present invention generally contain about 50 to 2500 ppm poly (oxyalkylene) amine and about 100 to 5000 ppm polyalkyl hydroxyaromatic compound. The ratio of polyalkyl hydroxyaromatic to poly (oxyalkylene) amine is generally in the range of about 0.5 to 10: 1, preferably about 2: 1 or higher.

The deposit control additive may be formulated as a concentrate with an inert, stable lipophilic organic solvent boiling in the range of about 150 ° F to 400 ° F. Benzene, toluene, xylene,
Alternatively, it is preferable to use an aliphatic or aromatic hydrocarbon solvent such as a higher boiling aromatic or aromatic thinner. Aliphatic alcohols having about 3 to 8 carbon atoms, such as isopropanol, isobutylcarbinol, n-butanol, etc., in combination with a hydrocarbon solvent are also suitable for use with the detergent-dispersant additive. . The amount of the additive composition according to the invention in the concentrate is usually at least 10% by weight, generally not more than 70% by weight and 10-50% by weight.
Is preferred, and 10 to 25% by weight is most preferred.

Gasoline fuels may contain other fuel additives such as anti-knock agents such as methylcyclopentadienyl manganese tricarbonyl, tetramethyl or tetraethyl lead, or other dispersants or detergents such as various substituted amines. May be. Also, aryl halides, for example,
A lead scavenger such as dichlorobenzene or an alkyl halide, eg ethylene dibromide, may be included. In addition, antioxidants, metal deactivators, pour point depressants, corrosion inhibitors, and demulsifiers may be present.

Other well known additives such as pour point depressants, flow improvers, cetane improvers and the like can be used in diesel fuel.

The following examples are provided to illustrate particular embodiments of the invention and are not intended to limit the scope of the invention in any way.

〔Example〕

Example 1 Preparation of polyisobutylphenol 203.2 g of phenol was placed in a flask equipped with a magnetic stirrer, a reflux condenser, a thermometer, a dropping funnel, and a nitrogen introducing tube. The phenol was warmed to 40 ° C and the heater was removed. Next 7
3.5 m of boron trifluoride etherate was added dropwise. Ultrabis 10 polyisobutene (molecular weight 950, obtained from British Petroleum, methyl vinylidene 76%)
It was dissolved in 1,863 m of hexane. 22 to polyisobutene
The reaction was added at a rate that maintained a temperature of 27 ° C. The reaction mixture was stirred at room temperature for 16 hours. Then 400 m concentrated ammonium hydroxide was added, followed by 2,000 m hexane. The reaction mixture was washed with water (3 x 2,000m), dried over magnesium sulphate, filtered and the solvent removed in vacuo to yield 1,056.5g of crude reaction product. The crude reaction product was purified by proton NMR and chromatographed on silica gel with hexane, then eluted with hexane: ethyl acetate: ethanol (93: 5: 2) to give the desired product.
% Was determined.

Example 2 Thermogravimetric Analysis The stability of certain fuel additives was measured by thermogravimetric analysis (TGA). The TGA method used a DuPont 951 TGA instrument connected to a microcomputer for data analysis. A sample of fuel additive (about 25 m) was heated from 25 ° C to 700 ° C at 5 ° C / min in a stream of air flowing at 100 cm ³ / min. The weight of the sample was detected as a function of temperature. The thermal stability of different samples was compared at 50% weight loss. Sample 1 is tetrapropenylphenyl poly (oxybutylene) ethylenediamine having a molecular weight of about 1718, prepared in a manner similar to that described in Examples 6-8 of US Pat. No. 4,160,648 by Lewis. It is a carbamate. Sample 2 was prepared in the same manner as in Example 1 above, using Ultrabis
Polyisobutylphenol prepared from 30 polyisobutene (molecular weight 1300, obtained from British Petroleum, methyl vinylidene 74%).

The 50% weight loss temperature of Sample 1, tetrapropenylphenyl poly (oxybutylene) ethylenediamine carbamate was 259 ° C. The 50% weight loss temperature of Sample 2, polyisobutylphenol was 347 ° C. A 1: 1 mixture of the two component samples 1 and 2 was analyzed by TGA. The 25% weight loss temperature [50% weight loss temperature of tetrapropenylphenyl poly (oxybutylene) ethylenediamine carbamate in the mixture] was 296 ° C. This indicates that the thermal stability of tetrapropenylphenyl poly (oxybutylene) ethylenediamine carbamate is increased by the presence of polyisobutylphenol. This increase in thermal stability allows the tetrapropenylphenyl poly (oxybutylene) ethylenediamine carbamate to last longer at the suction valve operating temperature and reduce deposits.

Example 3 Engine Test A laboratory engine test was used to evaluate deposit performance for both intake valves and combustion chambers of the additive compositions of the present invention. The test engine was a 4.3, TBI (Throttle Body Fuel Injection) V6 engine manufactured by General Motors.

The main engine specifications are listed below: The test method involved operating the engine for 40 hours (24 hours a day) according to specified weighting and speed plans that were representative of typical operating conditions. The engine operating process during the test is as follows: For all processes except process number 3, the conversion gradient (tr
ansition ramp). Step 3 included a 20 second conversion gradient.

All test experiments were performed with the same base gasoline, which represents a lead-free commercial fuel. The results are listed in Table III.

The results shown in Table III are for polyisobutylphenol and tetrapropenylphenyl poly (oxybutylene).
It has been shown that the combination with ethylenediamine carbamate has a synergistic effect, giving significantly better suction valve deposit control than with each component itself. Also, the addition of tetrapropenylphenyl poly (oxybutylene) ethylenediamine carbamate to polyisobutylphenol reduces the weight of combustion chamber deposits compared to polyisobutylphenol alone.

─────────────────────────────────────────────────── ─── Continuation of front page (56) References JP-A-52-155607 (JP, A) JP-B-62-31760 (JP, B1) JP-A-63-500602 (JP, A) (58) Field (Int.Cl. ⁷ , DB name) C10L 1/18 C10L 1/22

Claims (12)

(57) [Claims] 1. A poly (oxyalkylene) amine having at least one basic nitrogen atom, which is sufficient to render the poly (oxyalkylene) amine soluble in hydrocarbons boiling in the gasoline or diesel range. A poly (oxyalkylene) amine having a number of oxyalkylene units, and (b) a polyalkylhydroxyaromatic compound or salt thereof, wherein the polyalkyl group is a hydrocarbon boiling in the gasoline or diesel range. A fuel additive composition comprising a polyalkylhydroxy aromatic compound or a salt thereof having a molecular weight and a carbon chain length sufficient to make the compound soluble. 2. The fuel additive composition according to claim 1, wherein the poly (oxyalkylene) amine of component (a) has a molecular weight in the range of about 500 to about 10,000. 3. The fuel additive composition according to claim 1, wherein the poly (oxyalkylene) amine of component (a) has at least about 5 oxyalkylene units. 4. The fuel additive composition according to claim 1, wherein the poly (oxyalkylene) amine of component (a) is a hydrocarbyl poly (oxyalkylene) polyamine. 5. The fuel additive composition according to claim 1, wherein the poly (oxyalkylene) amine of component (a) is a hydrocarbyl poly (oxyalkylene) aminocarbamate. 6. The hydrocarbyl group of component (a) is from 1 to about 30.
The fuel additive composition of claim 5, having 6 carbon atoms. 7. The amino carbamate has an amine moiety of 2 to
The fuel additive composition according to claim 5, which is derived from a polyamine having 12 amine nitrogen atoms and 2 to 40 carbon atoms. 8. The fuel additive composition according to claim 1, wherein the polyalkyl hydroxyaromatic compound of component (b) has a polyalkyl group having an average molecular weight of about 400 to 5,000. 9. The fuel additive composition according to claim 1, wherein the hydroxyaromatic compound is phenol. 10. A poly-alpha substituent wherein the polyalkyl substituent of component (b) is polypropylene, polybutylene, or 1-decene.
The fuel additive composition according to claim 1, wherein the fuel additive composition is derived from an olefin oligomer. 11. A large amount of hydrocarbons boiling in the gasoline or diesel range and a detergent effective amount of (a) a poly (oxyalkylene) amine having at least one basic nitrogen atom in the gasoline or diesel range. A poly (oxyalkylene) amine having a sufficient number of oxyalkylene units to make the poly (oxyalkylene) amine soluble in a hydrocarbon boiling at, and (b) a polyalkylhydroxyaromatic compound or salt thereof, An addition of a polyalkylhydroxyaromatic compound or salt thereof, the polyalkyl group of which has a molecular weight and carbon chain length sufficient to make the polyalkylhydroxyaromatic compound soluble in hydrocarbons boiling in the gasoline or diesel range. A fuel composition comprising an agent composition. 12. An inert stable lipophilic organic solvent boiling in the range of about 150 ° F. to 400 ° F. and about 10-70% by weight of (a) at least one basic nitrogen atom. A poly (oxyalkylene) amine having a sufficient number of oxyalkylene units to solubilize the poly (oxyalkylene) amine in hydrocarbons boiling in the gasoline or diesel range, and (b ) A polyalkylhydroxyaromatic compound or salt thereof, wherein the polyalkyl group has a molecular weight and carbon chain length sufficient to solubilize the polyalkylhydroxyaromatic compound in hydrocarbons boiling in the gasoline or diesel range. A fuel concentrate comprising an additive composition comprising an alkyl hydroxy aromatic compound or a salt thereof.